Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
  • C01D15/00—Lithium compounds
  • C01D15/06—Sulfates; Sulfites
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
  • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
  • C01D5/02—Preparation of sulfates from alkali metal salts and sulfuric acid or bisulfates; Preparation of bisulfates
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
  • C01G1/10—Sulfates
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G45/00—Compounds of manganese
  • C01G45/02—Oxides
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G45/00—Compounds of manganese
  • C01G45/10—Sulfates
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G51/00—Compounds of cobalt
  • C01G51/04—Oxides
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G51/00—Compounds of cobalt
  • C01G51/10—Sulfates
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G53/00—Compounds of nickel
  • C01G53/04—Oxides
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G53/00—Compounds of nickel
  • C01G53/10—Sulfates
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G9/00—Compounds of zinc
  • C01G9/02—Oxides; Hydroxides
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G9/00—Compounds of zinc
  • C01G9/08—Sulfides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
  • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
  • C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B23/00—Obtaining nickel or cobalt
  • C22B23/04—Obtaining nickel or cobalt by wet processes
  • C22B23/0407—Leaching processes
  • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
  • C22B26/10—Obtaining alkali metals
  • C22B26/12—Obtaining lithium
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
  • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
  • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
  • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
  • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
  • C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
  • C22B3/1608—Leaching with acyclic or carbocyclic agents
  • C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
  • C22B3/1633—Leaching with acyclic or carbocyclic agents of a single type with oximes
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
  • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
  • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B47/00—Obtaining manganese
  • C22B47/0018—Treating ocean floor nodules
  • C22B47/0045—Treating ocean floor nodules by wet processes
  • C22B47/0054—Treating ocean floor nodules by wet processes leaching processes
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
  • C22B7/006—Wet processes
  • C22B7/007—Wet processes by acid leaching
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/54—Reclaiming serviceable parts of waste accumulators
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P10/00—Technologies related to metal processing
  • Y02P10/20—Recycling
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/84—Recycling of batteries or fuel cells

Definitions

• the process may produce any one or combination of crystalized nickel sulfate
• Example 5 e.g., see Copper Removal Circuit, Iron Removal, Cobalt/Manganese Solvent Extraction
• Example 5 and Fig. 7 e.g., see Iron Precipitation 1 and 2, Copper Cementation, Copper Ion Exchange
• Example 7 and Fig. 6 e.g., see Iron Removal
• the concentration of one or two metal sulfates are at a very low concentration in the PLS, and a third metal sulfate is at a much higher concentration
• careful selection of the crystallizer bleed rate e.g., a sufficiently high bleed rate
• crystallizer bleed rate can allow for selective crystallization of the third metal sulfate over the one or two metal sulfates.
• the process may use external sources of neutralizing agents (e.g., added oxides, hydroxides, etc.) in the refining stages to neutralize acids, and/or to basify the mother liquor bleed coming out of the crystallizer (also referred to herein as second neutralizing agents).
• external sources of neutralizing agents e.g., added oxides, hydroxides, etc.
• Selecting the type(s) and amount(s) of external neutralizing agent may depend, at least in part, on the nature of the refining stages, and the type of metal sulfate and other components in the mother liquor.
• electrolysis uses an applied electric potential and one or more ion selective membrane(s) to regenerate an acid and a base from a salt solution, and is conducted using an electrochemical cell that can comprise two or more compartments separated with selective membrane(s).
• the electrolysis may involve a 3-compartment cell operating under 6V of potential with a current density between 1500-3000 A/m 2 , which would be able to produce an approximately 20 wt% solution of sodium hydroxide along with an approximately 10 wt% solution of sulfuric acid from sodium sulfate, both of which can be recycled for use upstream in the process.
• the process described herein provides the selective co-crystallization of all three of crystalized nickel sulfate (N1SO 4 ), cobalt sulfate (C0SO 4 ), and manganese sulfate (MnSCU).
• the process described herein provides battery-grade, crystallized metal sulfates.
• the process provides electroplating-grade, crystallized metal sulfates.
• the process described herein does not use solvent extraction circuits to isolate battery-grade, crystallized metal sulfates.
• Copper Solvent Extraction recovered Copper from a pregnant leach solution flow of about 15 m 3 /h (PLS; see Leaching) before it underwent further treatment to recover nickel, cobalt and manganese.
• the extractant reagent used in this SX circuit was LIX 860N-I or an organic with similar properties.
• the copper-rich PLS was fed to an organic removal step to prevent residual organics from the black mass leaching coming into contact with the copper solvent extraction reagents which leads to contamination of the SX organic and degradation of performance. This was achieved by using a multi-media filter consisting of a structured packing to coalesce the bulk of the entrained organic.
• a crystallization step is then performed wherein metal sulfate, which comprises nickel sulfate, cobalt sulfate, and manganese sulfate, are crystallized from the aqueous solution to form crystallized metal sulfate in a mother liquor.
• the mother liquor also comprises an uncrystallized metal sulfate.
• the mother liquor is bled and the bleed rate is controlled to selectively inhibit crystallizing a lithium impurity when crystallizing the metal sulfate. In some variants of the method, this may result in crystallized metal sulfates that are substantially free of lithium.
• the crystallized metal sulfates may contain less than 2% by weight of lithium, or in some variants less than 1% or less than 0.5%.
• the basic metal salt is then used upstream of crystallizing the metal sulfate where it may be used as a neutralizing agent.
• the basifying step includes removing the basic metal salt from the mother liquor as a cake. For example, a first portion of the cake, e.g. up to 40%, may be used upstream when leaching the feedstock. Another portion of the cake, e.g. 60% or more, may be used in the refining stage, e.g. added in the Fe and Al removal stage. It is also possible to use the entire cake in the refining stage.
• the extractant used in this SX circuit is commercially available Cyanex 272 (Bis(2,4,4 Trimethlpentyl) Phosphenic Acid) diluted in a high flash point aliphatic solvent (referred through herein as the organic or organic extractant).
• the pregnant liquor was then fed to an Evaporative Crystallization Circuit that was operated under vacuum to flash cool the solution to 30°C. As the solution was flash cooled, more water was evaporated, forcing nickel sulphate salt to crystallize out of solution.
• the crystals were discharged from the crystallizer and fed to a centrifuge where they were dewatered and washed. The cake was discharged into a tank, where it was re-dissolved using hot condensate from the evaporator/crystallizer to a target concentration of Ni at 120 g/L .
• the impurities that accumulated in the Ni Crystallization mother liquor (such as magnesium, sodium, etc) were controlled via a process bleed which was monitored and purged to ensure that crystallized solids product requirements were achieved.
• Nickel Hydroxide Precipitation [00195] The raffinate from the Pre-Load Step and the nickel sulphate crystallizer bleed were fed to the Nickel Precipitation Circuit where sodium hydroxide was added to operate at pH of 8 which facilitated precipitation of nickel hydroxide.
• the circuit consisted of reactor train followed by a filtration unit. The filtrate and wash from filter press was transferred downstream to the Lithium Recovery Process.
• Table 4.0 lists the assumptions that formed the basis of the case study. Note that the price of sodium sulfate was assumed to be zero due to the challenges associated with its sale. Table 5.0 summarizes outcomes of the comparison. For typical flowsheets, operating costs were about 30% lower when ammonia was used instead of sodium hydroxide based on reagent cost assumptions. Combined with additional revenue assumed for the ammonium sulfate, this more than offset additional capital required to store liquid ammonia on site and resulted in an additional -300 million of NPV and -3% IRR.
• the resulting slurry was fed to the secondary centrifuge step where the product cake was washed prior to being combined with the primary product cake solids.
• the product cake was re-dissolved with demineralized water and pumped to the cathode production facility.
• the secondary centrate liquor was then fed to a polishing filtration step to remove any fine particulates prior to feeding a downstream Copper Removal Circuit.

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• Organic Chemistry (AREA)
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• Materials Engineering (AREA)
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• Electrochemistry (AREA)
• Geochemistry & Mineralogy (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Oceanography (AREA)
• Ocean & Marine Engineering (AREA)
• Manufacture And Refinement Of Metals (AREA)
• Inorganic Compounds Of Heavy Metals (AREA)
• Electroplating And Plating Baths Therefor (AREA)
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